Energy Efficient Emulsification using

Hydrophobically Modified
Alkali Swellable Amphipathic Polymers
Two Proprietary Rheology Modifiers
from 3V Inc.

Presented to the Midwest Chapter

of the Society of Cosmetic Chemists
January 13, 2015
https://nyscc.org/
A Primer on Emulsions
 Why emulsions?
• Delivery of active ingredients.

• Dilution of actives down to safe yet effective levels.

• Cost effective.

• Elegant aesthetics.

• Easy application.
 Definition
An emulsion is a dispersion of two or more
immiscible liquids.

• O/W (oil-in-water) - oil is the internal or

dispersed phase.

• W/O (water-in-oil) – oil is the external or

continuous phase.

• Multiple phase emulsions.

 Is it an emulsion or, something else?
Effect of Particle Size
• Dispersion Largest – least stable

• Suspension

• Emulsion

• Solution Smallest – most stable

 Types of emulsions
• Macroemulsions
– Dispersed phase 0.2-50 µ
– Kinetically stable but ultimately unstable due to the Second Law of
Thermodynamics.
– Opaque
– Relatively high energy input required

• Microemulsions
– Dispersed phase 0.01-0.2 µ
– Thermodynamically stable
– Transparent since droplet size <25% of wavelength of visible light
– Very low O/W interfacial tension due to very high surfactant levels
– Requires lower energy input
 Typical O/W Macro Emulsion
INGREDIENTS
[Wgt %] Funtionality
WATER PHASE
Water . . . . . . . . . . . . . . . . . 60-90 Diluent
Humectant . . . . . . . . . . . . . 2-7 Cushion, prevent drying out
Preservative . . . . . . . . . . . 0.05-0.5 Product protection
Surfactant . . . . . . . . . . . . . 0.25-2.0 Emulsifier for stability
Thickener . . . . . . . . . . . . . 0.1-0.75 Improved stability
Emollient . . . . . . . . . . . . . . 0.5-2.0 Elegant skin feel

OIL PHASE
Esters . . . . . . . . . . . . . . . . . 1.0-7.5 Elegant skin feel
Cosmetic Oils . . . . . . . . . . 2.0-10.0 Elegant skin feel
Surfactant . . . . . . . . . . . . . 1.0-5.0 Emulsifier for stability
OTC Actives . . . . . . . . . . . By law Sunscreens, etc.

OTHER
Preservative . . . . . . . . . . . 0.1-1.0 Product Protection
Perfume . . . . . . . . . . . . . . 0.1-1.0 Consumer Preference
 Factors Effecting Settling Velocity &
Emulsion Stability
Particle Suspending Medium
• count • density
• size • charge
• shape • Rheology
• density • polymer properties
• charge
 Rheology Modifiers
• Pseudoplastic
– Synthetic Polymers: Acrylic
Acid Polymers, Carbomers,
Hydrophobically Modifier
Polymers
– Gums: Guar, Hydroxypropyl
Guar, Xanthan, Carrageenan
– Clays: Hectorites, Bentonites,
Mg/Al Silicates
– Cellulosics: HEC, HPC
– Silicas: Hydrated Silicas,
Fumed Silicas
• Newtonian
– Polyethylene Glycols
• Thixotropic
– Gums: Karaya, Carrageenan
– Organoclays: Quaternium-18
Hectorites & Bentonites,
Stearalkonium Hectorites &
Bentonites, Disteardimonium
Hectorites
– Polyethylenes
– Silicas: Hydrated Silicas,
Fumed Silicas
– Trihydroxystearin
– Al/Mg Hydroxystearate
Viscosity vs. Typical Shear Rates Experienced by
Products

Newtonian
Pseudoplastic
Viscosity

Thixotropic

Shear Rate (s-1)

Storage Shipping  Dispensing  Application  Homogenization
 Why use rheology modifiers?

Stable Emulsions & Suspensions

Gravity

Yield Value Viscosity

Adopted from “The Rheology of Natural and Synthetic Hydrophilic Polymer Solutions as related to Suspending Ability” By
RJ Meyer and L. Cohen (BF Goodrich Chem. Co.) Presented in Nov. 1958, NYC. Published in Journal of Cosmetic Chemists
 Stokes Law
predictor of emulsion stability

V = 2r2g(D1-D2)/9µ

Where: V = the particle’s settling velocity (m/s)

r = the radius of the particle
g = the gravitational acceleration (m/s2)
D1 = the density of the particles (kg/m3)
D2 = the density of the fluid (kg/m3)
µ = the viscosity of the fluid (Pa s)

In words – A higher viscosity (denominator)

reduces the settling velocity. Therefore, the
emulsion or suspension will be more stable.
 Yield Value

Insufficient force Enough force to overcome

to induce flow yield value of the toothpaste

Yield Point (Pa) Viscosity (Pa·s)

Honey 0 11.0
Ketchup 14 0.1
Mayonnaise 85 0.6
 The Evolution of Emulsions

Water + Oil

Increasing emulsion stability & energy savings

WATER & OIL DON’T MIX
Significant energy input is
required to create a
homogeneous dispersion of
two immiscible liquids.
NEWS FLASH!

Once mixing stops syneresis,

coalescences, agglomeration,
creaming happens very quickly.
 The Evolution of Emulsions

Surfactants
Water + Oil

Increasing emulsion stability & energy savings

 Definition
• An emulsifier is a surface active agent (surfactant)
which reduces the interfacial tension between the
dispersed phase and the continuous phase.

• Emulsifiers may be also be hydrophilic colloids,

finely divided solids (e.g. Pickering Emulsions),
amphipathic polymers.
 The HLB System
Surfactant Selection
• Griffin 1947 Hydrophilic-Lipophilic Balance
• HLB of surfactant = mole % of hydrophilic
group / 5
• Maximum HLB = 20
• Required HLB of cosmetic oils
• Spans, Tweens, Poloxymers
 Bancroft’s Rule
• Where the emulsifier is the most soluble
becomes the external phase by lowering the
interfacial tension on that side of the film
• Hydrogen bonding between non-ionic
emulsifiers confers their rigidity and stability
to interfacial films why ethoxylated materials
are great emulsifiers
 Emulsion Preparation
• Energy input required to reduce droplet size of
internal/dispersed phase and create homogeneous
mixture
– Heat - increased temperature reduces viscosity and
decreases interfacial tension so favors emulsification over
coalescence
– Mechanical agitation
– Homogenization – high shear
– Ultrasonic vibration

• Amount of work depends upon length of time energy is

applied presence of emulsifiers
 April 22, 2015
45th Anniversary of Earth Day
What can YOU do to help save the
planet?
 Twelve Principles of Green Chemistry
1. Prevention - It’s better to prevent waste than to treat or clean up waste afterwards.
2. Atom Economy - Design synthetic methods to maximize the incorporation of all materials used in the
process into the final product.
3. Less Hazardous Chemical Syntheses - Design synthetic methods to use and generate substances that
minimize toxicity to human health and the environment.
4. Designing Safer Chemicals - Design chemical products to affect their desired function while minimizing
their toxicity.
5. Safer Solvents and Auxiliaries - Minimize the use of auxiliary substances wherever possible make them
innocuous when used.
6. Design for Energy Efficiency - Minimize the energy requirements of chemical processes and conduct
synthetic methods at ambient temperature and pressure if possible.
7. Use of Renewable Feedstocks - Use renewable raw material or feedstock rather whenever practicable.
8. Reduce Derivatives - Minimize or avoid unnecessary derivatization if possible, which requires additional
reagents and generate waste.
9. Catalysis - Catalytic reagents are superior to stoichiometric reagents.
10. Design for Degradation - Design chemical products so they break down into innocuous products that do
not persist in the environment.
11. Real-time Analysis for Pollution Prevention - Develop analytical methodologies needed to allow for real-
time, in-process monitoring and control prior to the formation of hazardous substances.
12. Inherently Safer Chemistry for Accident Prevention - Choose substances and the form of a substance used
in a chemical process to minimize the potential for chemical accidents, including releases, explosions, and
fires.
SOURCE: http://www.epa.gov/sciencematters/june2011/principles.htm
 Design for Energy Efficiency

6. Minimize the energy

requirements of chemical
processes and conduct synthetic
methods at ambient temperature
and pressure if possible.

SOURCE: http://www.epa.gov/sciencematters/june2011/principles.htm
 Dr. T.J. Lin
Lin, TJ, “Low-energy emulsification – I –
principles and applications”, J. Soc. Cosmet.
Chem., 29, p117-125, March 1978
Important Emulsion Variables to Control
• Components (ingredients) = cV
– Critical component of any emulsion are rheology
modifiers

• Process parameters and Equipment = pV

• Optimized emulsion property = Zp

“More is not always better. Sometimes, less is more.”

- Dr. TJ Lin
 LOW-ENERGY EMULSIFICATION (LEE)
A Conventional Hot Process B LEE

h
H External α Phase
Phase
h Internal Internal H β Phase
Phase Phase

h+H h + βH

Lin, Dr. TJ, Manufacturing Cosmetic Emulsions: Pragmatic Troubleshooting and Energy Conservation,
Allured Business Media, p. 124, 2010
 The Evolution of Emulsions

Low Energy Emulsification (LEE)

Surfactants
Water + Oil

Increasing emulsion stability & energy savings

Evolution of Emulsions
 Low Energy Emulsification
• Reduces the amount of energy required to
make a stable emulsion
• No need to change formula or buy new
equipment
• Reduces processing time and increase plant
capacity
• Saves money and reduces carbon footprint
 The Evolution of Emulsions

Non-Associative Polymers
e.g. Carbomer
LEE
Surfactants
Water + Oil

Increasing emulsion stability & energy savings

 Synthetic Polymeric Thickeners
(Homopolymers, Copolymers, Crosspolymers)
• Non-associative
– Carbomer
– Acrylates Copolymer
– Polyquaternium-37

“Carbomer is the ‘ultimate crutch’ to fix an unstable emulsion.”

– George Deckner
 Action Mechanism

Oil
Oil

Oil
Oil
Oil Oil

Carbomer “Alkylated” Carbomer

Traditional emulsion Polymeric emulsion
• Oil • Emulsifier • Oil • Water
• Water • Carbomer • Acrylates Vinyl Isodecanoate Crosspolymer

1. Increasing the viscosity of the continuous phase

2. Steric and electrostatic repulsion among drops
 The Evolution of Emulsions
Hydrophobically Modified Alkali-Swellable Polymers (HASPs)

Non-Associative Polymers
e.g. Carbomer
LEE
Surfactants
Water + Oil

Increasing emulsion stability & energy savings

 Synthetic Polymeric Thickeners
(Homopolymers, Copolymers, Crosspolymers)

• Non-associative
– Carbomer
– Acrylates Copolymer
– Polyquaternium-37
• Associative
 Associative Thickeners
Acrylates/Vinyl Isodecanoate Crosspolymer

Hydrophilic backbone
Thickening properties

= Carbon
= Oxygen
= Hydrogen

Lipophilic Moiety
Emulsifying properties
Resistance to electrolyte
Sensorial improvement
Higher Yield Value
 Mode of Action

Oil
Oil

Oil
Oil
Oil Oil

Carbomer “Alkylated” Carbomer

Traditional emulsion Polymeric emulsion
• Oil • Emulsifier • Oil • Water
• Water • Carbomer • Acrylates/Vinyl Isodecanoate Crosspolymer
1. Increasing the viscosity of the continuous phase
2. Steric and electrostatic repulsion among drops.
Higher BYV. Controlled release of oil phase actives.
 Simple Making Procedure
3 steps cold process  easy handling & cost
efficient

 Network building phase - dispersion and

swelling of the polymer particles in either the
water or oil phase

 Emulsification phase – addition of oil phase and

emulsification with continued agitation.
CAUTION: Avoid excessive shear to prevent
polymer breakdown and loss of viscosity.

 Neutralization - with a suitable agent

Evolution of Emulsions

Advantages: time saving, energy conservation and

increased production capacity
Acrylates / Vinyl Isodecanoate Crosspolymer
HLB Range Tested 7.5 - 13
 Associative Thickener
Acrylates/Vinyl Isodecanoate Crosspolymer
0.25% Polymer - 10% Oil - pH 6

Mineral Oil (HLB 10) Caprylic/Capric Triglyceride (HLB 11)

Up to 50% Up to 30%

C12-15 Alkyl Benzoate (HLB 13) Cyclopentasiloxane (HLB 7.5)

Up to 30% Up to 30%
 EFFECT OF OIL CONCENTRATION
0.25% Acrylates/Vinyl Isodecanoate Crosspolymer
(adjusted to pH 6 with NaOH)

15000 15000
mPa∙s

mPa∙s
10000 10000
5000 5000
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Mineral Oil % Caprylic/Capric Trigl. %
HLB 10 HLB 11

15000 15000
mPa∙s

mPa∙s
10000 10000
5000 5000
0 0
0 10 20 30 40 50 0 10 20 30 40 50
C12-15 Alkyl Benzoate % Cyclopentasiloxane %
HLB 13 HLB 7.5
 EFFECT OF ADDED EMULSIFIERS
15% C12-15 Alkyl Benzoate
0.25% Acrylates/Vinyl Isodecanoate Crosspolymer + 1% Emulsifier

LIPOPHILIC EMULSIFIERS NON-IONIC O/W EMULSIFIERS

mPa·s mPa·s
Cetearyl Alcohol 7200 Polysorbate-20 3300
Glyceryl Stearate 12000 Polysorbate-40 4250
Methyl Glucose SS 15000 Polysorbate-60 4300
Sorbitan Laurate 9800 Polysorbate-80 3700
Sorbitan Palmitate 14500 PEG-8 Stearate 8400
Sorbitan Stearate 31500 PEG-20 Stearate 4300
PEG-40 Stearate 4000
ANIONIC O/W EMULSIFIERS
PEG-100 Stearate 4500
K Cetyl Phosphate 4700 Ceteareth-20 3900
Na Cetearyl Sulfate 4750 Ceteareth-33 3900
 EFFECT OF TRADITIONAL EMULSIFIERS

Reduced oil droplet size and increased whiteness.

Lipophilic emulsifiers: high viscosity but a jelly-like consistency.
Hydrophilic emulsifiers: lower viscosity but excellent appearance.

Acrylates Vinyl Isodecanoate + 1% Polysorbate-60

Crosspolymer only
 Synthetic Polymeric Thickeners
(Homopolymers, Copolymers, Crosspolymers)
• Non-associative
– Carbomer
– Acrylates Copolymer
– Polyquaternium-37

• Associative
– Acrylates/Vinyl Isodecanoate Crosspolymer
 Acrylates/Palmeth-25 Acrylate Copolymer
Associative Polymeric Network

Hydrophobic
HASE =
alkylation
Hydrophobically
enhances
Modified
performance in
Alkali
many systems
Swellable Emulsion

HASE After
Neutralization
with Base

Drawing courtesy of Raymond Rigoletto

Acrylates/Palmeth-25 Acrylate Copolymer

Emulsion A
(Non-ionic)

Emulsion B
(Anionic)

Brookfield, RV 20 rpm, 25oC

Simple Emulsion Base A B

Ingredient Wgt % Wgt %
Cetearyl Glucoside & Cetearyl Alcohol 2.0 0.0
Ceteary Alcohol 0.0 2.0
Ethylhexyl Stearate 10.0 10.0
Dicaprylyl Ether 10.0 10.0
Caprylic/Capric Triglyceride 3.0 3.0
Potassium Cetyl Phosphate 0.0 0.5
Preserved Water QS to 100 % QS to 100%
Acrylates Palmeth-25 Acrylates Copolymer
HLB Range Tested 5-6 and 7.5-13
 Acrylates Palmeth-25 Acrylates Copolymer
Oils of different HLB requirements
10% Polymer + 30% Oil
Ingredient F G Cold Process
DI Water 56 56
Polymer (30%) 10 10 Procedure – Add polymer
C12-15 Alkyl Benzoate (HLB 13) 30 --- to water. Then add oil and
Cyclomethicone (HLB 7.5) --- 30 homogenize for 5 minutes
NaOH (10%) QS QS using Silverson L4RT-A at
100 100 4,000rpm. Neutralize with
pH 6.1 6.3 base to pH 6.25. 500 gram
Viscosity (cps) @ 25C 72,000 75,000 batch size.
Viscosity (cps) @45C 39,000 41,000
QS to pH 6.25 +/- 0.25
Brookfield RVT T-E spindle @ 10rpm

Photomicrographs 500X

10% Polymer + 30% C12-15 Alkyl Benzoate 10% Polymer + 30% Cyclomethicone
 Acrylates /Palmeth-25 Acrylates Copolymer
Effect of Increasing Oil Phase
10% Polymer & Mineral Oil increased from 20% to 40%
Ingredient Wgt % Wgt % Cold Process
DI Water 66 46
Polymer (30%) 10 10 Procedure – Add polymer to water. Add
M.O. 20 40 M.O. homogenizing for 5 minutes using
NaOH (5%) QS QS Silverson L4RT-A at 4,000rpm. Then
100 100 neutralize to about pH 6.5 with sweep
pH 6.5 6.7 agitation. 500 g batch size.
Viscosity (cps) @ 25C 34,500 106,000 Procedure – Dilute Batch B 50:50 with
Viscosity (cps) @ 45C 21,500 57,000 DI Water after the emulsion is formed.
QS to pH 6.25 +/- 0.25 5,000 cps @ 25C
Brookfield RVT T-E spindle @ 10rpm 1,000 cps @ 45C
Photomicrographs 500X

10% Polymer + 20% M.O. 10% Polymer + 40% M.O. 5% Polymer + 10% M.O.
(Batch B diluted 50:50)
 Acrylates /Palmeth-25 Acrylates Copolymer
Effect of Polymer Concentration
Decrease polymer concentration from 5.0% down to 1.25% keeping M.O. constant at 20%

Ingredients J K L Cold Process

Wgt % Wgt % Wgt %
DI Water 74.5 78.0 78.0 78.00 Procedure – Add polymer to water. Add
Polymer (30%) 5.0 2.5 1.25 M.O. homogenizing for 5 minutes using
M.O. 20.0 20.0 20.0 Silverson L4RT-A at 4,000rpm. Then
NaOH (5%) QS QS QS neutralize to about pH 6.5 with sweep
100.0 100.0 100.0 agitation. 500 g batch size.
pH 6.2 6.6 6.5
Viscosity (CPS) @ 25C 86,500 21,000 1,000
Viscosity (CPS) @ 45C 46,500 14,000 400
QS to pH 6.25 +/- 0.25
Brookfield RVT T-E spindle @ 10rpm Photomicrographs 500X

NOTE: A viscosity drop of 20%

for every 10C above 25C is a
general accepted norm.

5% Polymer 2.5% Polymer 1.25% Polymer

 Acrylates Palmeth-25 Acrylates Copolymer
Emulsification of Low HLB Oils
Ingredients Wgt % Wgt % Wgt %
DI Water 67.0 67.0 67.0 Cold Process
Polymer (30%) * 10.0 10.0 10.0 Procedure – Add polymer to
M.O. (HLB 10) 20.0 --- --- water. Add M.O.
Almond Oil (HLB 6) --- 20.0 --- homogenizing for 5 minutes
Dimethicone (HLB 5)) --- --- 20.0 using Silverson L4RT-A at
NaOH (5%) QS QS QS 4,000rpm. Then neutralize to
100.0 100.0 100.0 about pH 6.5 with sweep
pH 6.2 6.3 6.5 agitation. 500 g batch size.
Viscosity (cps) *** @ 25C 74,500 92,500 53,000
QS to pH 6.25 +/- 0.25
Brookfield RVT T-E spindle @ 10rpm

Photomicrographs 500X

Mineral Oil Almond Oil Dimethicone

HLB 10 HLB 6 HLB 5
 The Evolution of Emulsions
HASP Acrylates/Vinyl Isodecanoate Crosspolymer (powder)
Polymeric Acrylates/Palmeth-25 Acrylate Copolymer (liquid)
Emulsifiers
Non-Associative Polymers
e.g. Carbomer
LEE
Surfactants
Water + Oil

Increasing emulsion stability & energy savings

 The Greening of Emulsions
HASP Acrylates/Vinyl Isodecanoate Crosspolymer (powder)
Polymeric Acrylates/Palmeth-25 Acrylate Copolymer (liquid)
Emulsifiers
Non-Associative Polymers
e.g. Carbomer
LEE
Surfactants
Water + Oil

Increasing emulsion stability & energy savings

 Evolution of Emulsions

Advantages of Cold Process Emulsification: time saving, energy

conservation and increased production capacity
 One Pot Process Possible
• Acrylates/Vinyl Isodecanoate Acrylates Crosspolymer (powder)
– Direct Addition
• Add Polymer to Water Phase in main mix tank
• Add Oil Phase to the main mix tank with rapid agitation / homogenization
• Add suitable to neutralize to pH 5-7
– Indirect Method
• Add Polymer to Oil Phase in side kettle. Do not heat above 60oC
• Add Oil Phase to Water Phase containing sufficient neutralizing base to pH 5-7
with rapid agitation in main mix tank
• Do not over homogenize

• Acrylates/Palmeth-25 Acrylates Copolymer (liquid)

– Add Polymer to Water Phase in main mix vessel
– Add Oil Phase with homogenization
– Neutralize with suitable base to pH 6-7
 Acrylates Vinyl Isodecanoate Crosspolymer
• Properties
– Amphipathic polymer (powder form) for emulsification & thickening
– High suspending properties & improved electrolyte tolerance
– Enhanced water-resistance for sunscreen actives

• Applications
– O/W emulsions
– Clear styling gels
– Surfactant systems
– Clear hydroalcoholic hand sanitizers

• Easy to use
– May be dispersed either into water following the normal procedure for Carbomer or
into the Oil Phase of emulsions.
– Functional over a broad pH range. Neutralization can be carried out with alkali
(NaOH, KOH or NH4OH) or with hydrophilic organic amines (such as TEA, AMP,
TrisAmino).
Acrylates/Palmeth-25 Acrylate Copolymer
• Properties
– Hydrophobically modified associative thickener and emulsifier
– Liquid 30% polymer solids water-thin white emulsion

• Applications
– O/W emulsions
– Clear sulfate-free surfactant systems
– Styling products
– High pH products depilatories and relaxers

• Easy-to-use
– Adds instantly to water
 Review
Tips to Improve Emulsion Stability
• Prevent particle interaction
• Increase viscosity & yield value of continuous phase.
• Add polymer(s).
• Increase concentration of dispersed phase.
• Low levels of electrolytes.
• Reduce particle/droplet size of dispersed phase.
• Increase mechanical and/or heat energy.
• Emulsifier selection and concentration.
• Avoid aeration.
 SUMMARY
Hydrophobically modified amphipathic polymers are
one way to making even lower energy emulsions.
Cold process emulsification provides greater savings,
increased manufacturing capacity and . . .

Helps save the environment.

Marketing Sustainability

British Standard
from
Carbon Trust
3V cares about the environment
http://www.3vgreeneagle.com/en
 References
1. Lin, Dr. TJ, Manufacturing Cosmetic Emulsions: Pragmatic Troubleshooting
and Energy Conservation, Allured Business Media, 2010
2. Klein, Ken, Formulating Cosmetic Emulsions, SCC Continuing Education
Course, 1998.
3. Deckner, George and O’Lenick, Tony, Lamellar Gel Network Lab Workshop,
C&T Summit Philadelphia, June 2014
4. www.epa.gov, 12 Principals of Green Chemistry originally published by Paul
Anastas, Ph.D. and John Warner, Ph.D. in Green Chemistry: Theory and
Practice (Oxford University Press: New York, 1998),
5. “STABYLEN 30: A Thickening, Suspending and Emulsifying Agent for
Emulsions and Surfactant Systems”, 3V Technical Report No. 1 – Edition 2/1
6. “Formulation of O/W Emulsions with STABYLEN 30”, 3V Technical Report –
Edition 1/2
7. “SYNTHALEN® W2000: A Liquid Thickener for Cosmetic Applications”, 3V
Technical Report No. 6 - Edition 4/2